Pro-fragrances

ABSTRACT

The present invention relates to fragrance delivery systems which comprise: A) from about 0.01% by weight of a pro-fragrance component which comprises pro-fragrances or pro-accords selected from at least two of the following: i) aldehyde and ketone releasing pro-fragrances, preferably an oxazolidine pro-fragrance; ii) β-amino pro-fragrances; and iii) orthoester pro-accords; and B) the balance carries and others adjunct ingredients.

This application claims the benefit of provisional application No. 60/136,921 filed Jun. 1, 1999.

FIELD OF THE INVENTION

The present invention relates to fragrance delivery systems which comprise aldehyde and ketone releasing pro-fragrances, inter alia, oxazolidines, β-amino compounds, said pro-fragrances capable of delivering fragrance raw material aldehydes and ketones, to a situs, especially to human skin. The pro-fragrances of the present invention are formulatable with both other pro-fragrances and pro-accords as well as fragrance raw materials and pre-blended fragrance mixtures, for example, fragrance accords. The fragrance raw material delivery systems of the present invention provide the user with extended aesthetic benefits.

BACKGROUND OF THE INVENTION

Humans have applied scents and fragrances to their skin since antiquity. Originally these aesthetically pleasing materials were commonly isolated in raw form as resins, gums or essential oils from natural sources, inter alia, the bark, roots, leaves and fruit of indigenous plants. These resins, gums, and oils were directly applied to the body or diluted with water or other solvent, including in some cases, wine. With the advent of modern chemistry, individual components responsible for the odor properties of these resins, gums and oils were isolated and subsequently characterized. Aside from common “perfume vehicles” inter alia, fine perfumes, colognes, eau de toilettes, and after-shave lotions, a wide variety of personal care or personal hygiene items also deliver for aesthetic reasons fragrance notes, accords, or fragrance “characteristics”.

It is well known that mixtures of perfume or fragrance raw materials when deposited on the skin lose intensity and may change character with time, mainly due to factors such as differential evaporation and skin penetration. Many attempts have been made to minimize these drawbacks, but so far without notable success. Particularly, efforts have been made to prolong the diffusion, as well as to improve other characteristics of fragrance materials, by e.g. increasing the fragrance raw material concentration or by using additives such as silicones, glycerol, polyethylene glycols and so on. Such additions, however, have never been adequate to increase the longevity of the fragrance odor.

Recently the advent of pro-fragrance and pro-accords have afforded the fine fragrance and perfume formulator with the ability to deliver fragrance raw materials to human skin in a controllable manner thus enhancing the longevity of the fragrance. Most pro-accords inter alia orthoesters, are suitable for delivery of fragrance raw material alcohols and esters. Aldehydes and ketones have been delivered via acetals and ketals respectively, however, both of these pro-fragrance materials depend upon the modification of the carbonyl moiety and the rate of ketone fragrance raw material release has been difficult to fine tune to the subtleties of fine fragrance and perfume accords.

Accordingly, there remains a need in the art for a fragrance delivery system which is capable of delivering aldehyde and ketone fragrance raw material releasing pro-fragrance which can be formulated into fine fragrances, perfumes, personal care and personal hygiene products wherein the aldehyde and ketone fragrance raw material components can be released in a highly controllable manner to provide enhanced fragrance longevity.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned needs in that it has been surprisingly discovered that certain aldehyde fragrance raw materials, inter alia, para-t-bucinal, cymal, and lillial can be controllably released from novel heterocyclic pro-fragrances. The heterocyclic pro-fragrances, preferably oxazolidine pro-fragrances, of the present invention are useful in fragrance delivery systems which deliver fine fragrances with an enhanced perfume longevity.

A first aspect of the present invention relates to fragrance delivery systems which comprise pro-fragrances or pro-accords selected from at least two of the following:

-   -   i) aldehyde and ketone releasing pro-fragrances, preferably an         oxazolidine pro-fragrances;     -   ii) β-amino pro-fragrances; and     -   iii) orthoester pro-accords.

The fragrance delivery systems of the present invention comprise:

-   A) from about 0.01% by weight, of a pro-fragrance component     comprising:     -   a) optionally at least 0.01% by weight, of an aldehyde or ketone         releasing pro-fragrance component, said pro-fragrance having the         formula:         -   wherein said pro-fragrance or pro-accord releases an             aldehyde or a ketone fragrance raw material, wherein X is             oxygen or sulfur; R is:             -   i) C₆-C₂₂ substituted or unsubstituted linear alkyl;             -   ii) C₆-C₂₂ substituted or unsubstituted branched alkyl;             -   iii) C₆-C₂₂ substituted or unsubstituted linear alkenyl;             -   iv) C₆-C₂₂ substituted or unsubstituted branched                 alkenyl;             -   v) C₆-C₂₂ substituted or unsubstituted cycloalkyl;             -   vi) C₆-C₂₂ substituted or unsubstituted branched                 cycloalkyl;             -   vii) C₆-C₂₂ substituted or unsubstituted cycloalkenyl;             -   viii) C₆-C₂₂ substituted or unsubstituted branched                 cycloalkenyl ;             -   ix) C₆-C₂₂ substituted or unsubstituted aryl;             -   x) C₆-C₂₂ substituted or unsubstituted                 heterocyclicalkyl;             -   xi) C₆-C₂₂ substituted or unsubstituted                 heterocyclicalkenyl;             -   xii) and mixtures thereof;         -   R¹ is:             -   i) hydrogen;             -   ii) C₁-C₁₀ substituted or unsubstituted linear alkyl;             -   iii) C₃-C₁₀ substituted or unsubstituted branched alkyl;             -   iv) C₂-C₁₀ substituted or unsubstituted linear alkenyl;             -   v) C₃-C₁₀ substituted or unsubstituted branched alkenyl;             -   vi) C₃-C₁₅ substituted or unsubstituted cycloalkyl;             -   vii) C₄-C₁₅ substituted or unsubstituted branched                 cycloalkyl;             -   viii) C₄-C₁₅ substituted or unsubstituted cycloalkenyl;             -   ix) C₅-C₁₅ substituted or unsubstituted branched                 cycloalkenyl;             -   x) C₆-C₁₅ substituted or unsubstituted aryl;             -   xi) C₆-C₂₂ substituted or unsubstituted                 heterocyclicalkyl;             -   xii) C₆-C₂₂ substituted or unsubstituted                 heterocyclicalkenyl;         -   R and R¹ can be taken together to form a substituted or             unsubstituted ring having in the ring from 3 to 10 carbon             atoms; and         -   each R², R³, R⁶ and each R⁴ and R⁵ pair are independently:             -   i) R¹;             -   ii) hydroxyl;             -   iii) a carbonyl comprising unit having the formula:                 —(CH₂)_(x)COR⁷                 -   wherein R⁷ is:                 -    a) —OH;                 -    b) —OR⁸ wherein R⁸ is hydrogen, C₁-C₁₅ substituted                     or unsubstituted linear alkyl, C₁-C₁₅ substituted or                     unsubstituted branched alkyl, C₂-C₂₂ substituted or                     unsubstituted linear alkenyl, C₃-C₂₂ substituted or                     unsubstituted branched alkenyl, or mixtures thereof;                     or R⁸ is M, wherein M is a water soluble cation of                     sufficient charge to render neutrality;                 -    c) —N(R⁹)₂ wherein R⁹ is hydrogen, C₁-C₆                     substituted or unsubstituted linear alkyl, C₃-C₆                     substituted or unsubstituted branched alkyl, or                     mixtures thereof;                 -    d) C₁-C₂₂ substituted or unsubstituted linear                     alkyl;                 -    e) C₁-C₂₂ substituted or unsubstituted branched                     alkyl;                 -    f) C₂-C₂₂ substituted or unsubstituted linear                     alkenyl;                 -    g) C₃-C₂₂ substituted or unsubstituted branched                     alkenyl;                 -    h) C₃-C₂₂ substituted or unsubstituted cycloalkyl;                 -    i) C₆-C₂₂ substituted or unsubstituted aryl;                 -    j) C₆-C₂₂ substituted or unsubstituted                     heterocyclicalkyl;                 -    k) C₆-C₂₂ substituted or unsubstituted                     heterocyclicalkenyl;                 -    the index x is from 0 to 22;             -   iv) alkyleneoxy units having the formula:                 —(CR¹⁰R¹¹)_(y)(CHR¹²CHR¹³O)₂R¹⁴                 -   wherein each R¹⁰, R¹¹, and R¹² is independently;                 -    a) hydrogen;                 -    b) —OH;                 -    c) C₁-C₄ alkyl;                 -    d) or mixtures thereof;                 -   R¹³ is:                 -    a) hydrogen;                 -    b) C₁-C₄ alkyl;                 -    c) or mixtures thereof;                 -   R¹⁴ is:                 -    a) hydrogen;                 -    b) C₁-C₄ alkyl;                 -    c) or mixtures thereof;                 -   R¹⁰ and R¹¹ can be taken together to form a C₃-C₆                     spiroannulated ring, carbonyl unit, or mixtures                     thereof; y has the value from 0 to 10, z has the                     value from 1 to 50;             -   v) any two R², R³, R⁴, R⁵, or R⁶ units can be taken                 together to form:                 -   a) a carbonyl moiety;                 -   b) a C₃-C₆ spiroannulated ring;                 -   c) a heterocyclic aromatic ring comprising from 5 to                     7 atoms;                 -   d) a non-heterocyclic aromatic ring comprising from                     5 to 7 atoms;                 -   e) a heterocyclic ring comprising from 5 to 7 atoms;                 -   f) a non-heterocyclic ring comprising from 5 to 7                     atoms;                 -   g) or mixtures thereof;             -   vi) and mixtures thereof; and the index n is an integer                 from 1 to 3;     -   b) optionally at least 0.01% by weight, of an β-amino         pro-fragrance component, said pro-fragrance having the formula:         -   wherein G¹ is C₁-C₄ alkyl, —CN, —C(O)Y¹, —CO₂Y¹, Y², and             mixtures thereof; G² is C₁-C₄ alkyl —CN, —C(O)Y¹, —CO₂Y¹,             Y², and mixtures thereof; Y¹ and Y² are each independently             C₁-C₄ alkyl, or a unit having the formula:         -   wherein R⁶, R⁷, and R⁸ are each independently hydrogen,             C₁-C₄ alkyl, and mixtures thereof; R⁶ and R⁷ can be taken             together to form an exocyclic double bond with the ring; any             two R⁶ and R⁷, or an R⁶ and R⁷ with an R⁸ can be taken             together to form an endocyclic double bond within the ring;             two or more R⁶, R⁷, and R⁸ units may be taken together to             form one or more C₃-C₇ fused rings, bicyclic rings, or             spiroannular rings; m is from 1 to 5;         -   provided one G¹ or G² is —C(O)Y¹, —CO₂Y¹, or —CN; R and R¹             are each independently hydrogen, C₁-C₂₂ substituted or             unsubstituted, branched or unbranched alkyl, C₂-C₂₂             substituted or unsubstituted, branched or unbranched             alkenyl, C₂-C₂₀ substituted or unsubstituted, branched or             unbranched hydroxyalkyl, C₇-C₂₀ substituted or unsubstituted             alkylenearyl, C₃-C₂₀ substituted or unsubstituted             cycloalkyl, alkyleneoxy units having the formula:             —(R⁴O)_(x)R⁵         -   wherein R⁴ is C₂-C₄ alkylene, R⁵ is hydrogen, C₁-C₄ alkyl,             and mixtures thereof, x is from 1 to 6; C₆-C₂₀ aryl, C₅-C₂₀             heteroaryl comprising one or more heteroatoms selected from             the group consisting of nitrogen, oxygen, sulfur, and             mixtures thereof; R and R¹ can be taken together to form one             or more aromatic or non-aromatic, heterocyclic or             non-heterocyclic, single rings, fused rings, bicyclo rings,             spiroannulated rings, or mixtures thereof, said rings             comprising from 2 to 20 carbon atoms and one or more             heteroatoms selected from the group consisting of nitrogen,             oxygen, sulfur, and mixtures thereof;     -   c) optionally at least 0.01% by weight, of an orthoester         pro-accord having the formula:         -   wherein R is hydrogen, C₁-C₈ linear alkyl, C₄-C₂₀ branched             alkyl, C₆-C₂₀ cyclic alkyl, C₆-C₂₀ branched cyclic alkyl,             C₆-C₂₀ linear alkenyl, C₆-C₂₀ branched alkenyl, C₆-C₂₀             cyclic alkenyl, C₆-C₂₀ branched cyclic alkenyl, C₆-C₂₀             substituted or unsubstituted aryl, and mixtures thereof; R¹,             R² and R³ are independently C₁-C₂₀ linear, branched, or             substituted alkyl; C₂-C₂₀ linear, branched, or substituted             alkenyl; C₅-C₂₀ substituted or unsubstituted cyclic alkyl;             C₆-C₂₀ substituted or unsubstituted aryl, C₂-C₄₀ substituted             or unsubstituted alkyleneoxy; C₃-C₄₀ substituted or             unsubstituted alkyleneoxyalkyl; C₆-C₄₀ substituted or             unsubstituted alkylenearyl; C₆-C₃₂ substituted or             unsubstituted aryloxy; C₆-C₄₀ substituted or unsubstituted             alkyleneoxyaryl; C₆-C₄₀ oxyalkylenearyl, and mixtures             thereof; or a cyclic orthoester having the formula:         -   wherein at least one R⁴ or R⁵ is derived from a fragrance             raw material alcohol, each X is —C(R⁶)₂— wherein each R⁶ is             independently hydrogen, C₁-C₂₂ linear or branched alkyl,             C₂-C₂₂ linear or branched alkenyl, C₆-C₂₂ substituted or             unsubstituted aryl, and mixtures thereof, Y is —CR⁷R⁸—, C═O,             and mixtures thereof, wherein R⁷ and R⁸ are independently             hydrogen, hydroxyl, nitro, nitrilo, C₁-C₃₀ substituted or             unsubstituted linear alkyl, C₃-C₃₀ substituted or             unsubstituted branched alkyl, C₃-C₃₀ substituted or             unsubstituted cyclic alkyl, C₂-C₃₀ substituted or             unsubstituted linear alkenyl, C₃-C₃₀ substituted or             unsubstituted branched alkenyl, C₃-C₃₀ substituted or             unsubstituted cyclic alkenyl, C₂-C₃₀ substituted or             unsubstituted linear alkynyl, C₃-C₃₀ substituted or             unsubstituted branched alkynyl, C₆-C₃₀ substituted or             unsubstituted alkylenearyl, C₆-C₃₀ substituted or             unsubstituted aryl, C₂-C₂₀ substituted or unsubstituted             alkyleneoxy, C₃-C₂₀ substituted or unsubstituted             alkyleneoxyalkyl, C₇-C₂₀ substituted or unsubstituted             alkylenearyl, C₆-C₁₀ substituted or unsubstituted             alkyleneoxyaryl, and mixtures thereof, or R⁷ and R⁸ can be             taken together to form a spiroannulated ring or taken             together with any R⁶ form a fused ring, said spiroannulated             or fused ring having from 3 to 8 carbons and optionally one             or more heteroatoms in said ring, said ring further             optionally substituted by one or more C₁-C₂₂ alkyl C₁-C₂₂             alkenyl, C₆-C₁₂ aryl, C₆-C₂₂ alkylenearyl units, and             mixtures thereof; m is from 0 to 14, p is from 0 to 14, and             n is from 0 to 3; provided m+n+p is at least 1 and less than             or equal to 14; and -   B) optionally from about 1% by weight, a fragrance raw material     component comprising:     -   i) optionally at least 1% by weight, of a mixture of one or more         base note fragrances;     -   ii) optionally at least 1% by weight, of a mixture of one or         more top or middle note fragrances;     -   iii) optionally the balance carriers, fixatives, and other         adjunct ingredients.

These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to fragrance delivery systems which comprise at least two pro-fragrances or pro-accords wherein at least one pro-fragrance or pro-accord is selected from two of the following groups:

-   -   i) aldehyde and ketone releasing pro-fragrances, preferably an         oxazolidine pro-fragrances;     -   ii) β-amino pro-fragrances; and     -   iii) orthoester pro-accords.

Therefore, the fragrance delivery systems of the present invention comprise at least one pro-fragrance or pro-accord from group (i) and one from group (ii); or one from group (i) and one from (iii); or one from group (ii) and one from croup (iii). However, one or more pro-fragrances or pro-accords may be selected from each group or several from two groups.

One preferred embodiment comprises a fragrance delivery system which comprises all three pro-fragrance and pro-accords groups. Optionally, and preferably, the fragrance delivery systems of the present invention comprise other fragrance raw materials. In addition, the fragrance raw material delivery systems are typically admixed with one or more carriers or fixatives. The pro-fragrances and pro-accords of the present invention are suitable for use in fragrance delivery systems which are capable in delivering enhanced fragrance benefits to fine fragrances and perfumes as well as personal care and personal hygiene articles.

The following is a description of the essential pro-fragrances or pro-accords of the present invention.

Aldehyde and Ketone Releasing Pro-fragrances

The fragrance delivery systems of the present invention may comprise from about 0.01%, preferably from about 0.5%, more preferably from about 5%, most preferably from about 25% to about 99%, more preferably to about 75%, most preferably to about 50% by weight, of one or more heterocyclic aldehyde-releasing and/or ketone-releasing pro-fragrances, preferably oxazolidines, tertahydro-1,3-oxazines, thiazolidines, or tetrahydro-1,3-thiazines, more preferably oxazolidines, or tertahydro-1,3-oxazines, most preferably oxazolidines.

The pro-fragrances or pro-accords which are suitable for use in the fragrance delivery systems described herein have the formula:

and are capable of releasing an aldehyde fragrance raw material having the formula:

or a ketone fragrance raw material having the formula:

For the purposes of the fragrance delivery systems which comprise one or more heterocyclic pro-fragrances or pro-accords, R units are defined herein as:

-   -   i) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₅ substituted         or unsubstituted linear alkyl; one or more examples of a         fragrance raw material which comprises this unit includes         nonanal and decanal;     -   ii) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₅         substituted or unsubstituted branched alkyl; one or more         examples of a fragrance raw material which comprises this unit         includes 2-methyldecanal;     -   iii) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₅         substituted or unsubstituted linear alkenyl; one or more         examples of a fragrance raw material which comprises this unit         includes 10-undecenal;     -   iv) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₅         substituted or unsubstituted branched alkenyl; one or more         examples of a fragrance raw material which comprises this unit         includes citral, melonal, and neral;     -   v) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₀ substituted         or unsubstituted cycloalkyl; one or more examples of a fragrance         raw material which comprises this unit includes         cyclopentadecanone;     -   vi) C₆-C₂₂, preferably C₆-C₁₅, more preferably C₆-C₁₅         substituted or unsubstituted branched cycloalkyl; one or more         examples of a fragrance raw material which comprises this unit         includes camphor and muscone;     -   vii) C₆-C₂₂, preferably C₆-C₁₈ more preferably C₆-C₁₅         substituted or unsubstituted cycloalkenyl; one or more examples         of a fragrance raw material which comprises this unit includes         civetone;     -   viii) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₅         substituted or unsubstituted branched cycloalkenyl; one or more         examples of a fragrance raw material which comprises this unit         includes α-damascone and β-ionone;     -   ix) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₀         substituted or unsubstituted aryl wherein said aryl unit         preferably comprises a phenyl unit; one or more examples of a         fragrance raw material which comprises this unit includes         benzldehyde, hydrotropaldehyde and vanillin;     -   x) C₆-C₂₂, preferably C₆-C₁₅, more preferably C₆-C₁₅ substituted         or unsubstituted heterocyclicalkyl;     -   xi) C₆-C₂₂, preferably C₆-C₁₈, more preferably C₆-C₁₅         substituted or unsubstituted heterocyclicalkenyl; one or more         examples of a fragrance raw material which comprises this unit         includes;     -   xii) and mixtures thereof;         -   R¹ is:             -   i) hydrogen;             -   ii) C₁-C₁₀, preferably C₁-C₅ substituted or                 unsubstituted linear alkyl;             -   iii) C₃-C₁₀, preferably C₃-C₅ substituted or                 unsubstituted branched alkyl;             -   iv) C₂-C₁₀, preferably C₂-C₅ substituted or                 unsubstituted linear alkenyl;             -   v) C₃-C₁₀, preferably C₄-C₁₀ substituted or                 unsubstituted branched alkenyl;             -   vi) C₃-C₁₅, preferably C₆-C₁₀ substituted or                 unsubstituted cycloalkyl;             -   vii) C₄-C₁₅, preferably C₆-C₁₀ substituted or                 unsubstituted branched cycloalkyl;             -   viii) C₄-C₁₅, preferably C₆-C₁₀ substituted or                 unsubstituted cycloalkenyl;             -   ix) C₅-C₁₅, preferably C₆-C₁₀ substituted or                 unsubstituted branched cycloalkenyl;             -   x) C₆-C₁₅, preferably C₆-C₁₀ substituted or                 unsubstituted aryl;             -   xi) C₆-C₂₂, preferably C₆-C₁₀ substituted or                 unsubstituted heterocyclicalkyl;             -   xii) C₆-C₂₂, preferably C₆-C₁₀ substituted or                 unsubstituted heterocyclicalkenyl;         -   R and R¹ can be taken together to form a substituted or             unsubstituted ring having in the ring from 3 to 10 carbon             atoms; one or more examples of which are substituted             cyclopentanone derivatives inter alia hedione and nectaryl;             and         -   each R², R³, R⁶ and each R⁴ and R⁵ pair are independently:             -   i) R¹;             -   ii) hydroxyl;             -   iii) a carbonyl comprising unit having the formula:                 —(CH₂)_(x)COR⁷                 -   wherein R⁷ is:                 -    a) —OH, in the case of carboxylic acids;                 -    b) —OR⁸, in the case of esters wherein R⁸ is                     hydrogen; C₁-C₁₅, preferably C₁-C₁₀, more preferably                     C₁-C₄ substituted or unsubstituted linear alkyl;                     C₃-C₁₅, preferably C₃-C₁₀, more preferably C₃-C₄                     substituted or unsubstituted branched alkyl; C₂-C₂₂,                     preferably C₂-C₁₀, more preferably C₂-C₄ substituted                     or unsubstituted linear alkenyl; C₃-C₂₂ substituted                     or unsubstituted branched alkenyl, or mixtures                     thereof; or R⁸ is a cation, M, having sufficient                     charge to provide electronic neutrality, preferably                     M is sodium, potassium, and ammonium;                 -    c) —N(R⁹)₂ in the case of amides wherein each R⁹ is                     independently hydrogen; C₁-C₁₅, preferably C₁-C₁₀,                     more preferably C₁-C₄ substituted or unsubstituted                     linear alkyl; C₃-C₁₅, preferably C₃-C₁₀, more                     preferably C₃-C₄ substituted or unsubstituted                     branched alkyl; or mixtures thereof;                 -    d) C₁-C₂₂, preferably C₁-C₅ substituted or                     unsubstituted linear alkyl;                 -    e) C₁-C₂₂, preferably C₃-C₅ substituted or                     unsubstituted branched alkyl;                 -    f) C₂-C₂₂, preferably C₂-C₅ substituted or                     unsubstituted linear alkenyl;                 -    g) C₃-C₂₂, preferably C₄-C₁₀ substituted or                     unsubstituted branched alkenyl;                 -    h) C₅-C₂₂, preferably C₆-C₁₀ substituted or                     unsubstituted cycloalkyl;                 -    i) C₆-C₂₂, preferably C₆-C₁₀ substituted or                     unsubstituted aryl;                 -    j) C₆-C₂₂, preferably C₆-C₁₀ substituted or                     unsubstituted heterocyclicalkyl;                 -    k) C₆-C₂₂, preferably C₆-C₁₀ substituted or                     unsubstituted heterocyclicalkenyl;                 -    the index is from 0 to 22;             -   v) alkyleneoxy units having the formula:                 —(CR¹⁰R¹¹)_(y)(CHR¹²CHR¹³O)_(z)R¹⁴                 -   wherein each R¹⁰, R¹¹, and R¹² is independently;                 -    a) hydrogen;                 -    b) —OH;                 -    c) C₁-C₄ alkyl, preferably methyl;                 -    d) or mixtures thereof; preferably R¹⁰, R¹¹, and                     R¹² are each hydrogen;                 -   R¹³ is:                 -    a) hydrogen;                 -    b) C₁-C₄ alkyl, preferably methyl;                 -    c) or mixtures thereof; preferably R¹³ is methyl or                     hydrogen, more preferably hydrogen;                 -   R¹⁴ is:                 -    a) hydrogen;                 -    b) C₁-C₄ alkyl, preferably methyl;                 -    c) or mixtures thereof; preferred R¹⁴ is hydrogen;

R¹⁰ and R¹¹ can be taken together to form a C₃-C₆ spiroannulated ring, carbonyl unit, or mixtures thereof, y has the value from 0 to 10, z has the value from 1 to 50;

-   -   -   -   vi) any two R², R³, R⁴, R⁵, or R⁶ units can be taken                 together, and where feasible, combined to form:                 -   a) a carbonyl moiety;                 -   b) a C₃-C₆ spiroannulated ring;                 -   c) a heterocyclic aromatic ring comprising from 5 to                     7 atoms;                 -   d) a non-heterocyclic aromatic ring comprising from                     5 to 7 atoms;                 -   e) a heterocyclic ring comprising from 5 to 7 atoms;                 -   f) a non-heterocyclic ring comprising from 5 to 7                     atoms;                 -   g) or mixtures thereof;             -   vii) and mixtures thereof;             -   the index n is an integer from 1 to 3, preferably 1 or                 2, more preferably 1.

For the purposes of the present invention, the term “substituted” is defined herein as “compatible moieties which replace a hydrogen atom”. For the purposes of the present invention, hydrogens which are substitutable are labeled as R′ units in the following examples. Non-limiting examples of substituents which can replace hydrogen atoms are C₁-C₂₂ linear or branched hydrocarbyl units, inter alia, alkyl, alkenyl; hydroxy, nitrilo, nitro, carboxyl (—CHO; —CO₂H; —CO₂R″; —CONH₂; —CONHR″; —CONR″₂; wherein R″ is C₁-C₁₂ linear or branched alkyl), amino, C₁-C₂₂ mono- and dialkylamino, and mixtures thereof. However, the formulator may wish to include other substituents not specifically mentioned herein. Not each hydrogen of a substituted unit, i.e., substituted linear alkyl, must be substituted; only one hydrogen must be substituted by another moiety for a unit to be “substituted” for the purposes of the present invention.

A non-limiting example of a preferred aldehyde and ketone releasing pro-fragrance has the general formula:

non-limiting examples of which include the pro-fragrances having the formula:

-   -   d) and mixtures thereof.         β-Amino Pro-fragrances

The fragrance delivery systems of the present invention may comprise from about 0.01%, preferably from about 0.5%, more preferably from about 5%, most preferably from about 25% to about 99%, more preferably to about 75%, most preferably to about 50% by weight, of one or more β-amino pro-fragrances, preferably ionone and damascone releasing β-amino pro-fragrances.

The β-amino pro-fragrances of the present invention have the formula:

wherein G¹ is C₁-C₄ alkyl, —CN, —C(O)Y¹, —CO₂Y¹, Y², and mixtures thereof; G² is C₁-C₄ alkyl, —CN, —C(O)Y¹, —CO₂Y¹, Y², and mixtures thereof; Y¹ and Y² are each independently C₁-C₄ alkyl, or a unit having the formula:

wherein R⁶, R⁷, and R⁸ are each independently hydrogen, C₁-C₄ alkyl, and mixtures thereof; preferably methyl; or alternatively any pair of R⁶ and R⁷ can be taken together to form an exocyclic double bond with the ring; any two adjacent R⁶ and R⁷ units, or alternatively an R⁶ or R⁷ unit with an adjacent R⁸ unit can be taken together to form an endocyclic double bond within the ring, preferred compounds comprising endocyclic double bonds include C₆ hydrocarbyl units which include cycloalkyl and cycloalkenyl moieties, inter alia, damascones and ionones, further described herein below; or two or more R⁶, R⁷, and R⁸ units from any ring carbon may be taken together to form one or more C₃-C₇ fused rings, bicyclic rings, or spiroannular rings; provided one G¹ or G² is —C(O)Y¹, —CO₂Y¹, or —CN. The index m is from 1 to 5; preferably m is 4 which provides a cyclohexyl ring.

Beyond the requirement that at least one G¹ or ² unit comprise a —C(O)Y¹, —CO₂Y¹, or —CN unit, preferred G¹ and G² units are C₁-C₄ alkyl, preferably methyl; and a unit wherein Y¹ is selected from the group consisting of:

-   -   i) 2,6,6-trimethylcyclohex-2-enyl having the formula:     -   ii) 2,6,6-trimethylcyclohex-1-enyl having the formula:     -   iii) 2-methylene-6,6-dimethylcyclohexanyl having the formula:     -   iv) 2,6,6-trimethylcyclohex-3-enyl having the formula:     -   v) and mixtures thereof.

Further non-limiting examples of Y¹ and Y² units include 4,6,6-trimethylcyclohex-1-enyl; 2,2-dimethylcyclohexyl; 2,2,4-trimethylcyclohexyl; 2,2,6-trimethylcyclohexyl; 2,2-dimethyl-3-methylene-6-methylcyclohexanyl; 2,2,3,6-tetramethylcyclohexanyl; 2-methyl-6,6-dimethylhexa-1,3-dienyl; 4-methyl-6,6-dimethylhexa-1,3-dienyl; and mixtures thereof.

R and R¹ are each independently hydrogen, C₁-C₂₂ substituted or unsubstituted, branched or unbranched alkyl, C₂-C₂₂ substituted or unsubstituted, branched or unbranched alkenyl, C₂-C₂₀ substituted or unsubstituted, branched or unbranched hydroxyalkyl, C₇-C₂₀ substituted or unsubstituted alkylenearyl, C₃-C₂₀ substituted or unsubstituted cycloalkyl, alkyleneoxy units having the formula: —(R⁴O)_(x)R⁵ wherein R⁴ is C₂-C₄ alkylene, R⁵ is hydrogen, C₁-C₄ alkyl, and mixtures thereof, x is from 1 to 6; C₆-C₂₀ aryl, C₅-C₂₀ heteroaryl comprising one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and mixtures thereof; R and R¹ can be taken together to form one or more aromatic or non-aromatic, heterocyclic or non-heterocyclic, single rings, fused rings, bicyclo rings, spiroannulated rings, or mixtures thereof, said rings comprising from 2 to 20 carbon atoms and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and mixtures thereof.

The following are the common chemical names for the damascones and ionones which are delivered by the pro-fragrances of the present invention; 1-(2,6,6-trimethylcyclohex-2-enyl)-2-butene-1-one (α-damascone), 1-(2,6,6-trimethylcyclohex-1-enyl)-2-butene-1-one (β-damascone), 1-(2-methylene-6,6-dimethylcyclohexanyl)-2-butene-1-one (γ-damascone), 1-(2,6,6-trimethylcyclohex-3-enyl)-2-butene-1-one (δ-damascone), 4-(2,6,6-trimethylcyclohex-2-enyl)-3-butene-2-one (α-ionone), 4-(2,6,6-trimethylcyclohex-1-enyl)-3-butene-2-one (β-ionone), 4-(2-methylene-6,6-dimethylcyclohexanyl)-3-butene-2-one (γ-ionone).

Further preferred ketones which can be delivered by the β-amino ketone pro-fragrances of the present invention include 4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-methyl-3-buten-2-one, 1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptandien-3-one, 4-(2,5,6,6-tetramethyl-2-cyclohexen-yl)-3-methyl-3-buten-2-one, 2-pentyl-2-cyclopenten-1-one, 2-hexyl-2-cyclopenten-1-one, cis-3-methyl-2-(2-pentenyl)-2-cyclopenten-1-one, 6-(2-propenyl)-5-methyl-2(1-methylethylidene)cyclohexanone, 4-(4-methoxy)phenyl-3-buten-2-one, 2,5,5-trimethyl-2,6-heptadien-4-one, and 2-methyl-6-(4-methylcyclohex-3-enyl-2,5-heptadien-4-one.

Non-limiting examples of β-amino pro-fragrances according to the present invention include 1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N-(2-hydroxyethyl)-N-phenylmethyl-1-butanone having the formula:

1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-di(2-hydroxyethyl)-1-butanone having the formula:

1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(5-hydroxy-3-oxapentyl)-1-butanone having the formula:

and 2-hexyl-3-di(2-hydroxyethyl)aminocyclopentanone having the formula:

Orthoester Pro-accords

The fragrance delivery systems of the present invention optionally comprise optionally from about 0.01%, preferably from about 0.5%, more preferably from about 5%, most preferably from about 25% to about 99%, more preferably to about 75%, most preferably to about 50% by weight, of an orthoester pro-accord having the formula:

wherein R is hydrogen, C₁-C₈ linear alkyl, C₄-C₂₀ branched alkyl, C₆-C₂₀ cyclic alkyl, C₆-C₂₀ branched cyclic alkyl, C₆-C₂₀ linear alkenyl, C₆-C₂₀ branched alkenyl, C₆-C₂₀ cyclic alkenyl, C₆-C₂₀ branched cyclic alkenyl, C₆-C₂₀ substituted or unsubstituted aryl, and mixtures thereof;R¹, R² and R³ are independently C₁-C₂₀ linear, branched, or substituted alkyl; C₂-C₂₀ linear, branched, or substituted alkenyl; C₅-C₂₀ substituted or unsubstituted cyclic alkyl; C₆-C₂₀ substituted or unsubstituted aryl, C₂-C₄₀ substituted or unsubstituted alkyleneoxy; C₃-C₄₀ substituted or unsubstituted alkyleneoxyalkyl; C₆-C₄₀ substituted or unsubstituted alkylenearyl; C₆-C₃₂ substituted or unsubstituted aryloxy; C₆-C₄₀ substituted or unsubstituted alkyleneoxyaryl; C₆-C₄₀ oxyalkylenearyl, and mixtures thereof; or a cyclic orthoester having the formula:

wherein at least one R⁴ or R⁵ is derived from a fragrance raw material alcohol, each X is —C(R⁶)₂— wherein each R⁶ is independently hydrogen, C₁-C₂₂ linear or branched alkyl, C₂-C₂₂ linear or branched alkenyl, C₆-C₂₂ substituted or unsubstituted aryl, and mixtures thereof, Y is —CR⁷R⁸—, C═O, and mixtures thereof, wherein R⁷ and R⁸ are independently hydrogen, hydroxyl, nitro, nitrilo, C₁-C₃₀ substituted or unsubstituted linear alkyl, C₃-C₃₀ substituted or unsubstituted branched alkyl, C₃-C₃₀ substituted or unsubstituted cyclic alkyl, C₂-C₃₀ substituted or unsubstituted linear alkenyl, C₃-C₃₀ substituted or unsubstituted branched alkenyl, C₃-C₃₀ substituted or unsubstituted cyclic alkenyl, C₁-C₃₀ substituted or unsubstituted linear alkynyl, C₃-C₃₀ substituted or unsubstituted branched alkynyl, C₆-C₃₀ substituted or unsubstituted alkylenearyl, C₆-C₃₀ substituted or unsubstituted aryl, C₂-C₂₀ substituted or unsubstituted alkyleneoxy, C₃-C₂₀ substituted or unsubstituted alkyleneoxyalkyl, C₇-C₂₀ substituted or unsubstituted alkylenearyl, C₆-C₁₀ substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof, or R⁷ and R⁸ can be taken together to form a spiroannulated ring or taken together with any R⁶ to form a fused ring, said spiroannulated or fused ring having from 3 to 8 carbons and optionally one or more heteroatoms in said ring, said ring further optionally substituted by one or more C₁-C₂₂ alkyl, C₁-C₂₂ alkenyl, C₆-C₁₂ aryl, C₆-C₂₂ alkylenearyl units, and mixtures thereof; m is from 0 to 14, p is from 0 to 14, and n is from 0 to 3; provided m+n+p is at least 1 and less than or equal to 14.

Non-limiting examples of alcohols suitably released by the orthoester pro-accords include methanol, 2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5,6-dimethyl-1-methylethenylbicyclo[2.2.1]hept-5-ene-2-methanol (Arbozol), 2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo geraniol), 4-(1-methylethyl)cyclohexanemethanol (Mayol), α-3,3-trimethyl-2-norborane methanol, 1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methanol, ethanol, 2-phenylethanol, 2-cyclohexyl, ethanol, 2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, 2-(p-methylphenyl)ethanol, 6,6-dimethylbicyclo-[3.1.1]hept-2-ene-2-ethanol (nopol), 2-(4-methylphenoxy)ethanol, 3,3-dimethyl-Δ²-β-norbornane ethanol, 2-methyl-2-cyclohexylethanol, 1-(4-isopropylcyclohexyl)-ethanol, 1-phenylethanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2-(4-methyl-phenyl)ethanol, n-propanol, 2-propanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic Alcohol), 2-(cyclododecyl)propan-1-ol (Hydroxy-ambran), 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2-propen-1-ol (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-1-ol (methylcinnamyl alcohol), α-n-pentyl-3-phenyl-2-propen-1-ol (α-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4-methylphenyl)-2-propanol, n-butanol, 2-butanol, 3-methylbutanol, 3-(4-methylcyclohex-3-ene)butanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)butanol, 2-ethyl-4-(2,2,3-trimethylcyclopent-3-enyl)-2-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, 3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)butan-2-one, pentanol, cis-3-pentenol, 3-methyl-pentanol, 3-methyl-3-penten-1-ol, 2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-5-phenylpentanol, 2-methyl-5-(2,3-dimethyltricyclo[2.2.1.0(2,6)]hept-3-yl)-2-penten-1-ol (santalol), 4-methyl-1-phenyl-2-pentanol, (1-methyl-bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-ol, 3-methyl-1-phenylpentan-3-ol, 1,2-dimethyl-3-(1-methylethenyl)cyclopentan-1-ol, 2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isoproenyl-4-methyl-4-hexen-1-ol (Lavandulol), 2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene (Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol (carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol, 1-methyl-4-iso-propenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol, 2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 4-isopropyl-cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol, 2-(5,6,6-trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-ol, heptanol, 2,4-dimethylheptan-1-ol, 2,4-dimethyl-2,6-heptandienol, 6,6-dimethyl-2-oxymethylbicyclo[3.1.1]hept-2-ene (myrtenol), 4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 3,6-methyl-3-vinyl-5-hepten-2-ol, 6,6-dimethy-3-hydroxy-2-methylenebicyclo[3.1.1]heptane, 1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2,6-dimethylheptan-2-ol, 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol (myrcenol), 7-methyloctan-1-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol (geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 3,7-dimethyl-1,6-octadien-3-ol (linalool), 3,7-dimethyloctan-1-ol (pelagrol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-1-ol, 3,7-dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-5,7-otadien-2-ol, 4,7-methyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan-3-ol, 3,6-dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5-octadien-2-ol (muguol), 3-methyl-1-octen-3-ol, 7-hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol, cis-6-nonen-1-ol, 6,8-dimethylnonan-2-ol, 3-(hydroxymethyl)-2-nonanone, 2-nonanone-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonadien-3-ol, decanol, 9-decenol, 2-benzyl-M-dioxa-5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 4-methyl-3-decen-5-ol, 3,7,9-timethyl-1,6-decadien-3-ol (isobutyl linallol), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodece-1-ol, 2,4-dodecadien-1-ol, 2,7,11-trimethyl-2,6,10-dodecatrien-1-ol (famesol), 3,7,11-trimethyl-1,6,10-dodecatrien-3-ol, 3,7,11,15-tetramethylhexadec-2-en-1-ol (phytol), 3,7,11,15-tetramethylhexadec-1-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), para-cymen-7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl alcohol, methyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4-(1-propenyl)phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl-ortho-hydroxy benzoate, ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5-methoxy-1-methylbenzene, 2-tert-butyl-4-methyl-1-hydroxybenzene, 1-ethoxy-2-hydroxy-4-propenylbenzene, 4-hydrozytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2-naphthol, 1,3,3-trimethyl-2-norbornanol (fenchol), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-ol, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-ol, 2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuran, β-caryophyllene alcohol, and mixtures thereof.

Preferred pro-accords are selected from the group consisting of tris-geranyl orthoformate, tris(cis-3-hexen-1-yl)orthoformate, tris(phenylethyl)orthoformate, bis(citronellyl)ethyl orthoacetate, tris(citronellyl)orthoformate, tris(cis-6-nonenyl)orthoformate, tris(phenoxyethyl)orthoformate, tris(geranyl, neryl)orthoformate (70:30 geranyl neryl), tris(9-decenyl)orthoformate, tris(3-methyl-5-phenylpentanyl)orthofornate, tris(6-methylheptan-2-yl)orthoformate, tris([4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-yl]orthofonrate, tris[3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-yl]orthoformate, trismenthyl orthoformate, tris(4-isopropylcyclohexylethyl-2-yl)orthoformate, tris-(6,8-dimethylnonan-2-yl)orthoformate, tris-phenylethyl orthoacetate, tris(cis-3-hexen-1-yl)orthoacetate, tris(cis-6-nonenyl)orthoacetate, tris-citronellyl orthoacetate, bis(geranyl)benzyl orthoacetate, tris(geranyl)orthoacetate, tris(4-isopropylcyclohexylrnethyl)orthoacetate, tris(bezyl)orthoacetate, tris(2,6-dimethyl-5-heptenyl)orthoacetate, bis(cis-3-hexen-1-yl)amyl orthoacetate, and neryl citronellyl ethyl orthobutyrate, nonadyl orthoformate, mugetanol orthoformate, osyrol orthofoniate, undecavertol orthoformate and mixtures thereof.

Orthoester pro-accords and pro-fragrances and the fragrance raw materials which they are capable of delivering, all of which are suitable for inclusion in the fragrance delivery systems of the present invention, described in U.S. Pat. No. 6,013,618 Morelli et al., issued Jan. 11, 2000; U.S. Pat. No. 5,919,752 Morelli et al., issued Jul. 6, 1999 both of which are incorporated herein by reference.

FRAGRANCE DELIVERY SYSTEMS

The present invention also relates to fragrance raw material delivery systems which can be fully formulated and used without dilution. Preferably said delivery systems are diluted with one or more carriers. Alternatively, and in an equally preferable embodiment, the fragrance delivery systems of the present invention can be combined with other fragrance raw materials.

After formulation or combination with other fragrance raw materials and carriers, the fragrance delivery systems of the present invention can be formulated into compositions, inter alia, deodorants, shampoos, fine fragrances.

The fragrance delivery systems of the present invention comprise:

-   -   i) optionally from about 0.01%, preferably from about 0.5%, more         preferably from about 5%, most preferably from about 25% to         about 99%, more preferably to about 75%, most preferably to         about 50% by weight, of a cyclic aldehyde or ketone releasing         pro-fragrance as described herein above;     -   ii) optionally from about 0.01%, preferably from about 0.5%,         more preferably from about 5%, most preferably from about 25% to         about 990% more preferably to about 75%, most preferably to         about 50% by weight, of an β-amino pro-fragrance component         according to the present invention;     -   iii) optionally from about 0.01%, preferably from about 0.5%,         more preferably from about 5%, most preferably from about 25% to         about 99%, more preferably to about 75%, most preferably to         about 50% by weight, of one or more pro-accords formed from at         least one fragrance raw material, wherein said pro-accord is an         orthoester, and     -   iv) optionally the balance carriers, stabilizers, and other         adjunct ingredients; however, one compound from two of (i),         (ii), or (iii) must be present.

Non-limiting examples of the fragrance delivery system of the present invention are illustrated by the following:

TABLE I Weight % Ingredients 1 2 3 4 β-Amino ketone pro-fragrance¹ 50 40 — — β-Amino ketone pro-fragrance² — — — 60 Pro-fragrance³ 25 20 — — Pro-fragrance⁴ 25 20 45 — Pro-fragrance⁵ — — 55 20 Carrier⁶ — balance — balance ¹1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(5-hydroxy-3-oxapentyl)-1-butanone. ²1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N-(5-hydroxy-3-oxapentyl)-1-butanone. ³2-(2,4-dimethyl-3-cyclohexen-1-yl)-3-(1-methylethyl)4-oxazolidinecarboxylic acid methyl ester. ⁴2-(6-methyl-5-hepten-2-yl)-3-(1-methylethyl)-4-oxazolidinecarboxylic acid methyl ester. ⁵Tris(geranyl) orthoformate. ⁶Ethanol. Further examples of the use of the fragrance delivery systems of the present invention include delivery systems comprising:

-   A) from about 0.1%, preferably from about 0.5%, more preferably from     about 1%, yet more preferably from about 5%, most preferably from     about 10% to about 100%, preferably to about 75%, more preferably to     about 50% by weight, of at least two pro-fragrance or pro-accord     components selected from the group comprising:     -   i) optionally from about 0.01%, preferably from about 0.5%, more         preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of a cyclic aldehyde or ketone releasing         pro-fragrance as described herein above;     -   ii) optionally from about 0.01%, preferably from about 0.5%,         more preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of an β-amino pro-fragrance component         according to the present invention;     -   iii) optionally from about 0.01%, preferably from about 0.5%,         more preferably from about 5%, most preferably from about 25% to         about 99%, more preferably to about 75%, most preferably to         about 50% by weight, of one or more pro-accords formed from at         least one fragrance raw material, wherein said pro-accord is an         orthoester;     -   iv) the balance carriers, stabilizers, and other adjunct         ingredients; and -   B) optionally from about 0.01%, preferably from about 0.5%, more     preferably from about 1%, yet more preferably from about 5%, most     preferably from about 10% to about 99%, preferably to about 75%,     more preferably to about 50% by weight, a fragrance raw material     component comprising:     -   i) optionally at least 0.01%, preferably from about 0.5%, more         preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of a mixture of one or more base note         fragrances;     -   ii) optionally at least 0.01%, preferably from about 0.5%, more         preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of a mixture of one or more top or middle         note fragrances;     -   iii) optionally the balance carriers, fixatives, and other         adjunct ingredients.

A non-limiting example of a preferred embodiment of the fragrance delivery system of the present invention includes:

-   A) from about 0.1%, preferably from about 0.5%, more preferably from     about 1%, yet more preferably from about 5%, most preferably from     about 10% to about 100%, preferably to about 75%, more preferably to     about 50% by weight, of at least two pro-fragrance or pro-accord     components selected from the group comprising:     -   i) optionally from about 0.01%, preferably from about 0.5%, more         preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of a cyclic aldehyde or ketone releasing         pro-fragrance as described herein above;     -   ii) optionally from about 0.01%, preferably from about 0.5%,         more preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of an β-amino ketone pro-fragrance         component according to the present invention;     -   iii) optionally from about 0.01%, preferably from about 0.5%,         more preferably from about 5%, most preferably from about 25% to         about 99%, more preferably to about 75%, most preferably to         about 50% by weight, of one or more pro-accords formed from at         least one fragrance raw material, wherein said pro-accord is         selected from the group consisting of acetals, ketals,         orthoesters, orthocarbonates, and mixtures thereof, each         pro-accord releasing upon hydrolysis said fragrance raw material         from which it is formed, said fragrance raw materials selected         from the group consisting of primary, secondary, and tertiary         alcohols, aldehydes, ketones, esters, carbonates, and mixtures         thereof, provided at least one pro-accord:         -   a) is formed from at least one fragrance raw material having             a molecular weight greater than or equal to about 100 g/mol;         -   b) has a fragrance release half-life of greater than or             equal to about 0.1 hound pH 5.3 and less than or equal to             about 12 hours at pH 2.5 when measured in NaH₂PO₄ buffer;     -   iv) the balance carriers, stabilizers, and other adjunct         ingredients; and -   B) optionally from about 0.01%, preferably from about 0.5%, more     preferably from about 1%, yet more preferably from about 5%, most     preferably from about 10% to about 99%, preferably to about 75%,     more preferably to about 50% by weight, of a fragrance raw material     component comprising:     -   i) optionally at least 0.01%, preferably from about 0.5%, more         preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of a mixture of one or more base note         fragrances;     -   ii) optionally at least 0.01%, preferably from about 0.5%, more         preferably from about 5%, most preferably from about 25% to         about 100%, more preferably to about 75%, most preferably to         about 50% by weight, of a mixture of one or more top or middle         note fragrances;     -   iii) optionally the balance carriers, fixatives, and other         adjunct ingredients.

When used the fragrance delivery systems of the present invention will comprise from about 0.1%, preferably from about 1% to about 100%, preferably to about 85% of the composition depending upon the execution. For example, a fine fragrance may comprise 100% by weight, of a fragrance delivery as described herein, whereas a body lotion or cream may comprise from about 1% to about 5% by weight, of the fragrance delivery system.

For the purposes of the fragrance delivery systems of the present invention, a “pro-accord which comprises n fragrance raw materials but which releases n+1 fragrance raw materials” is defined as “a compound which is prepared from one or more fragrance raw materials, said fragrance raw material being chemically transformed into a “releasable form” such that when said releasable form breaks down, the original fragrance raw material is released as well as at least one other fragrance raw material which was not a starting material used in forming the releasable form”. The term “releasable form” is defined herein as a “pro-fragrance or pro-accord compound, which ever form is applicable”. Non-limiting examples of “releasable forms” or pro-accords which satisfy the n+1 requirement are as follows.

Preferably the pro-accords of the present invention are orthoesters and orthocarbonates which deliver n+1 fragrance raw materials when the “pro-accord” has been formed from n fragrance raw materials. These “Increased Release” pro-accords are preferably formate, acetate, propionate, and benzoate orthoesters. Any fragrance raw material may be used to form the “increased release” pro-accord provided the final pro-accord:

-   -   a) has a molecular weight greater than or equal to about 300         g/mol;     -   b) has a molecular weight at least two times greater than the         lowest molecular weight fragrance raw material which comprises         said pro-accord; and     -   c) has a fragrance release half-life greater than or equal to         about 0.1 hours when measured in NaH₂PO₄ buffer at pH 5.3 and         less than about 12 hours when measured in NaH₂PO₄ buffer at pH         2.5.         The value of the index n is an integer from 1 to 3.

When present the “increased release” pro-accords comprise at least 0.01% of the increased fragrance retention composition, preferably at least about 0.1% more preferably at least about 0.5% by weight, of said composition. More than one “increased release” pro-accords may be combined together as described herein above to provide a complex perfume mixture or accord.

The pro-accord tris(9-decenyl) orthoformate is prepared by treating 9-decenol (i.e., Rosalva), which is a fragrance raw material as defined herein, with a suitable amount of triethyl orthoformate, not a fragrance raw material as defined herein, in the presence of an acid catalyst optionally in the presence of a solvent. Tris(9-decenyl) when exposed to suitable conditions (e.g., exposure to the acid mantle of human skin) breaks down to release a mixture of 9-decenol and 9-decenyl formate, both of which are fragrance raw materials. Therefore, one fragrance raw material is used to prepare a releasable form (pro-accord) of two fragrance raw materials.

The pro-accord 3,7-dimethyl-1,6-octadien-3-yl 3(β-naphthyl)-3-oxo-propionate, which is a β-ketoester pro-accord, is prepared by treating 3,7-dimethyl-1,6-octadien-3-ol (linalool), which is a fragrance raw material according to the present invention, with diketene under suitable conditions to form intermediate 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, which is subsequently treated with 2-naphthoyl chloride to yield the pro-accord. 3,7-Dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate when exposed to suitable conditions (e.g., exposure to nascent moisture) breaks down to release a mixture of linalool and methyl β-naphthyl ketone, both of which are fragrance raw materials as defined herein.

As described herein above, an optional component of the fragrance delivery systems of the present invention are pro-fragrances or pro-accords which are not heterocyclic aldehyde and/or ketone releasing pro-fragrances. The optional pro-accords or pro-fragrances are equally functional in either personal care compositions inter alia lotions, creams, deodorants or personal fragrance compositions inter alia fine fragrances, perfumes.

Preferred optional pro-accords and/or pro-fragrances include, but are not limited to, orthocarbonates, acetals, ketals, ortholactones, and β-ketoesters.

Non-limiting examples of optional orthocarbonates which are suitable for use in the fragrance delivery systems of the present invention include bis(ethyl) bis(geranyl) orthocarbonate, bis(ethyl) bis(phenylethyl) orthocarbonate, bis(ethyl) bis(cis-3-hexenyl) orthocarbonate, bis(ethyl) bis(citronellyl) orthocarbonate, bis(ethyl) bis(linalyl) orthocarbonate, bis(ethyl) bis(menthyl) orthocarbonate, bis(dodecyl) bis(geranyl) orthocarbonate, and bis(dodecyl) bis(phenylethyl) orthocarbonate.

Non-limiting examples of optional acetals which are suitable for use in the fragrance delivery systems of the present invention include bis(cis-3-hexenyl) vanillin, bis(geranyl) cinnamaldehyde acetal, bis(2-phenylethyl) anisaldehyde acetal, bis (citronellyl) cyclamen aldehyde acetal, and bis(citronellyl) citral acetal.

Non-limiting examples of optional ketals which are suitable for use in the fragrance delivery systems of the present invention include bis(linalyl) β-ionone ketal, bis(dihydromyrcenyl) α-damascone ketal, bis(linalyl) 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone ketal, bis(dihydromyrcenyl) β-ionone ketal, and bis(citronellyl) cis-jasmone ketal.

Non-limiting examples of optional β-ketoesters which are suitable for use in the fragrance delivery systems of the present invention include 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(α-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, cis 3-hexen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2,2-dimethylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(βnaphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-(β-naphthyl)-3-oxo-propionate, and 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate.

An example of a fragrance delivery system according to the present invention comprises:

-   -   a) from about 0.1% by weight, of a β-amino ketone pro-fragrance         selected from the group consisting of         1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(5-hydroxy-3-oxapentyl)-1-butanone,         1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(2-hydroxyethyl)-1-butanone,         1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N-(5-hydroxy-3-oxopentyl)-1-butanone,         and mixtures thereof;     -   b) from about 0.2% by weight, of one or more aldehyde releasing         pro-fragrances, for example,         2-(6-methyl-5-hepten-2-yl)-3-(1-methylethyl)-4-oxazikudubecarboxylic         acid methyl ester,         2-(2,4-dimethyl-3-cyclohexen-1-yl)-3-(1-methylethyl)-4-oxazolidinecarboxylic         acid methyl ester;     -   c) optionally from about 0.1% by weight, of one or more alcohol         releasing pro-fragrances; preferably an alcohol releasing         pro-accord, for example, geranyl orthoformate;     -   d) from about 0.1% by weight, of one or more fragrance raw         materials, for example, lillial, γ-decalactone;     -   e) optionally, from about 1% by weight, of pre-blended perfume         ingredients of fragrance raw material accords; and     -   f) the balance carriers.

A non-limiting example of an alcohol releasing pro-accord admixture which is suitable for use in the fragrance delivery systems of the present invention comprises:

-   -   i) from about 0.5% to about 5% by weight, of nonadyl         orthoformate;     -   ii) from about 1.5% to about 5% by weight, of mugetanol         orthoformate;     -   iii) from about 1.5% to about 5% by weight, of osyrol         orthoformate; and     -   iv) from about 1% to about 10% by weight, of benzyl         orthoacetate.         Fragrance Release Half-life

One aspect of the present invention which is a key element in providing the formulator with a method for determining the manner in which a pro-fragrance according to the present invention releases its fragrance raw material, is the measurement of the pro-fragrance “Fragrance Release Half-Life, (FRHL). The pro-fragrances useful in the personal care compositions of the present invention generally have a delayed release of final fragrance raw material in order to achieve the increased fragrance longevity benefits described herein. However, the pro-fragrances generally also deliver the fragrance raw materials during a time period useful to the formulator, for example, within a time period desirable to the consumer.

For the purposes of the present invention the pro-accords generally have a FRHL of less than or equal to 12 hours when measured in NaH₂PO₄ buffer at pH 2.5 and greater than or equal to 0.1 hour when measured in NaH₂PO₄ buffer at pH 5.3. The “Fragrance Release Half-life” is defined herein as follows.

Pro-fragrances deliver their corresponding mixture of fragrance raw materials or fragrance accords according to the equation: Pro-Fragrance→Fragrance Raw Material wherein the fragrance raw material which is released may be released as a single component or a multiple fragrance raw material accord.

The rate at which the fragrance is released is defined by the formula: Rate=k[Pro-fragrance] and can be further expressed by the formula: ${- \frac{\mathbb{d}\left\lbrack {{Pro}\text{-}{fragrance}} \right\rbrack}{\mathbb{d}t}} = {k\left\lbrack {{Pro}\text{-}{fragrance}} \right\rbrack}$ wherein k is the release rate constant and [Pro-fragrance] is the concentration of pro-fragrance. For the purposes of the present invention the “Fragrance Release Half-life”, t_(1/2), is related to the release rate constant by the formula: $t_{1/2} = \frac{0.693}{k}$ and this relationship is used for the purposes of the present invention to determine the” FRHL.

Due to the hydrophobic nature of some pro-accords, it is necessary to conduct the determination of t_(1/2) and k in a mixture of 90/10 dioxane/phosphate buffered water. The phosphate buffered water is prepared by admixing 3.95 mL of 85% phosphoric acid (H₃PO₄) and 24 g of sodium dihydrogen phosphate (NaH₂PO₄) with one liter of water. The pH of this solution is approximately 2.5. Next 10 mL of the phosphate buffer is admixed with 90 mL of dioxane and the pro-fragrance to be analyzed is added. The hydrolysis kinetics are then monitored by conventional HPLC at 30° C.

In some instances, it is desirable to formulate a fragrance delivery system having one or more pro-fragrances which deliver a rapid release of fragrance raw material in addition to the delayed onset of a fragrance. In such cases the hydrolysis rate, and therefore the determination of t_(1/2) must be measured in a buffer system which can accommodate this more rapid hydrolysis rate.

The pro-fragrances of the present invention are stable under pH conditions encountered in the formulation and storage of fine perfume, personal care and personal hygiene articles which have a pH of from about 7.1 to 11.5, and during solution-use of such products. Due to their high molecular weight and hydrophobicity, these pro-fragrances and/or pro-accords remain deposited upon skin even when exposed to water (i.e. when formulated into a sun screen). Because the pro-fragrances are subject to hydrolysis when the pH is reduced, they hydrolyze to release their component fragrance compounds when applied to skin or are exposed even to reduced pH such as present in air and humidity. The reduction in pH should be at least 0.1, preferably at least about 0.5 units. Preferably the pH is reduced by at least 0.5 units to a pH of 7.5 or less, more preferably 6.9 or less. Preferably, the solution in which the pro-accord is applied is alkaline.

Odor Value

The pro-fragrances of the present invention typically have an Odor Value greater than or equal to about 1, preferably greater than or equal to about 5, more preferably greater than or equal to about 10. The term “Odor Value” is defined by the following formula: ${OV} = \frac{\left\lbrack {{Concentration}\quad{of}\quad{FRM}} \right\rbrack}{ODT}$ wherein OV is the odor value of the fragrance raw material released upon the skin by the pro-accord. The odor value is the concentration of the fragrance raw material, FRM, on the skin, surface divided by the Odor Detection Threshold, ODT. The term “level of noticeability” is often applied to and/or substituted for the term “odor value”. Odor Detection Threshold

For the purposes of the present invention the term “odor detection threshold” is defined as the level at which a fragrance raw material is perceptible to the average human. The odor detection threshold (ODT) of the compositions of the present invention are preferably measured by carefully controlled gas chromatograph (GC) conditions as described hereinbelow. The preferred fragrance raw materials of the present invention have an ODT of at least about 100 part per billion (ppb), more preferably 10 ppb, most preferably 1 ppb. Fragrance raw materials having an ODT greater than 10 parts per million (ppm) are typically avoided unless useful as an adjunct ingredient, for example, as an adjunct alcohol when adjusting the fragrance release half-life of an orthoester.

Determination of Odor Detection Thresholds is as follows. A gas chromatograph is characterized to determine the exact volume of material injected by a syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution. The air flow rate in accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material. To determine whether a material has a threshold below 10 ppb, solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is notice. The average over all panelists determines the threshold of noticeability or ODT. The necessary amount of analyte is injected onto the column to achieve a 10 ppb concentration at the detector. Typical gas chromatograph parameters for determining odor detection thresholds are listed below.

-   GC: 5890 Series II with FID detector 7673 Autosampler -   Column: J&W Scientific DB-1, length 30 m, i.d. 0.25 mm, film     thickness 1 μm. -   Split Injection: 17/1 split ratio -   Autosampler: 1.13 μl/injection -   Column flow: 1.10mL/min -   Air flow: 345 mL/min -   Inlet temperature: 245° C. -   Detector temperature: 285° C. -   Temperature Information:     -   Initial temperature: 50° C.     -   Rate: 5° C./min     -   Final temperature: 280° C.     -   Final time: 6 min -   Leading assumptions: 0.02 minutes per sniff and that GC air adds to     sample dilution.     Skin Performance Index

Although a pro-fragrance or pro-accord may comprise a fragrance release half-life which ensures delivery of a fragrance raw material during a period of time useful to the formulator, unless the fragrance raw materials which comprise said fragrance delivery system have ODT values large enough to be perceived by the user, the formulator will be compelled to use an inordinate amount of material to achieve a suitable fragrance level.

The pro-fragrances of the present invention have a Skin Performance Index (SPI) greater than or equal to 0.1, preferably greater than or equal to 0.5. The Skin Performance Index is defined by the following: ${SPI} = \frac{\left\lbrack {{Odor}\quad{Value}} \right\rbrack^{*}}{t_{1/2}}$ wherein the term [Odor Value]* is the estimated concentration of the fragrance raw material in the headspace above a solution of the fragrance raw material as measured in a 1% solution of ethanol, and t_(1/2) is the fragrance release half-life measured at pH 5.3 in the above described buffer. For the purposes of the present invention, the t_(1/2) of the SPI is measured at 5.3 and the value of the fragrance release half-life is preferably from 0.1 hours to 60 hours.

The [Odor Value]* is an estimation of the vapor pressure of the fragrance raw material using empirically determined KOVATS indices. “The Vapor Pressures of Pure Substances”, T. Boublik et al., Elseiver, N.Y. (1973) incorporated herein by reference, describes an index line for normal alkanes wherein C₁₀ is equal to 30,000 ppb, C₁₂ is equal to 3,000 ppb, C₁₄ is equal to 300 ppb, C₁₆ is equal to 30 ppb, etc. Using these values as reference standards, the KOVATS index of a fragrance raw material is obtained from gas chromatographic analysis of the FRM and the experimental index is then used to determine the relative vapor pressure and hence the head space concentration of the fragrance raw material.

“New Method for Estimating Vapor Pressure by the Use of Gas Chromatography” J. Chromatography A, 79 p 123-129, (1996) and “Simple and Versatile Injection System for Capillary Gas Chromatographic Columns: Performance Evaluation of a System Including Mass Spectrometric and Light Pipe Fourier-Transform Infrared Detection”, J. Chromatography A, 713, p 201-215, (1996) included herein by reference, further describe methods and techniques suitable for use in determining the vapor pressure and head space concentration of FRM's as they relate to the term [Odor Value]* of the present invention.

Using the criteria set forth in the present invention inter alia fragrance release half-life, odor value, odor detection threshold, skin performance index, the formulator is able to fashion an aldehyde or ketone releasing cyclic pro-fragrance. By manipulation of the R², R³, R⁴, R⁵ and R⁶ units of the cyclic pro-fragrances of the present invention, the release rate of either an aldehyde or ketone fragrance raw material can be adjusted. Several different pro-fragrances which release the same fragrance raw material, but at differing rates or levels, can be admixed to further prolong or extend the period of fragrance raw material delivery.

When present, the carriers, fixatives, or stabilizers will comprise the balance of the compositions. Typical carriers are methanol, ethanol preferred), iso-propanol, polyethylene glycol, as well as water in some instances, especially as a vehicle to deliver materials which provide reserve alkalinity to the fragrance delivery system. Fixatives serve to lower the volatility of certain top and middle notes in order to extend their contact time on skin. Adjunct ingredients include perfume raw material components which are essential oils and are therefore not a single chemical entity. In addition, the adjunct ingredients may be mixtures of materials which serve a purpose in addition to providing a pleasurable odor (i.e., an astringent in a personal hygiene article).

The formulators, in addition to selected fragrance raw materials, can combine a pre-blended fragrance with the pro-fragrances of the present invention. For the purposes of the present invention the term “pre-blended fragrance” is defined as an existing fragrance accord, commercially available or otherwise, which is enhanced by or in turn enhances the fragrance delivered by the pro-fragrances and/or pro-accords which comprise the balance of the fragrance delivery system. For example, an existing fragrance accord may be suitable in the short term but due to differential evaporation of the most volatile components, high notes, inter alia, the fragrance diminishes or the bouquet shifts. Therefore, pro-fragrances and pro-accords are a combined which will release said volatile components thereby sustaining the complete fragrance accord.

The following is a non-limiting example of a β-amino ketone pro-fragrance according to the present invention.

EXAMPLE 5 1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N-(2-hydroxyethyl)-N-phenylmethyl-1-butanone

The damascone releasing ε-amino ketone pro-fragrance adduct is prepared by stirring 1 equivalent of δ damascone with 2 equivalents of N-benzylethanolamine until complete as indicated suitable analytical method inter alia, thin layer chromatography, ¹H NMR. The product is purified by column chromatography on Aluminum Oxide (activated, basic, Brockman I, standard grade, 150 mesh, 58 angstrom) using a mobile phase consisting of 50% hexane, 49% chloroform and 1% triethylamine. Solvents are removed in vacuo and the product is placed under high vacuum (0.10 mm Hg) for 24 hours with stirring to remove any residual solvent to yield the desired β-amino ketone pro-fragrance.

The following are examples of fine fragrance compositions which comprise the fragrance delivery system of the present invention.

TABLE II Weight % Ingredients 6 7 8 9 β-Amino ketone pro-fragrance¹ 0.4 0.8 — — β-Amino ketone pro-fragrance² — — — 0.6 Pro-fragrance³ 0.2 0.4 — — Pro-fragrance⁴ 0.2 0.4 0.5 — Pro-fragrance⁵ — — 0.6 0.2 Pro-fragrance⁶ — — — 0.2 Pre-formulated accords⁷ 14.0 14.0 14.0 14.0 Fragrance raw material⁸ 1.98 1.98 — — Fragrance raw material⁹ 0.02 0.02 — — Carrier¹⁰ balance balance balance balance ¹1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(5-hydroxy-3-oxapentyl)-1-butanone. ²1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N-(5-hydroxy-3-oxapentyl)-1-butanone. ³2-(2,4-dimethyl-3-cyclohexen-1-yl)-3-(1-methylethyl)4-oxazolidinecarboxylic acid methyl ester. ⁴2-(6-methyl-5-hepten-2-yl)-3-(1-methylethyl)-4-oxazolidinecarboxylic acid methyl ester. ⁵Tris(geranyl) orthoformate. ⁶Benzyl bis(geranyl) orthoformate. ⁷Admixture of one or more fragrance raw materials which is enhanced by the presence of said fragrance delivery system. ⁸Lillial. ⁹γ-decalactone. ¹⁰Ethanol.

TABLE III Weight % Ingredients 10 11 12 13 β-Amino ketone pro-fragrance¹ — — — 0.6 β-Amino ketone pro-fragrance² 0.4 0.8 — — Pro-fragrance³ 0.2 0.3 — — Pro-fragrance⁴ 0.2 0.3 1.0 — Pro-fragrance⁵ — — 0.8 — Pro-fragrance⁶ — — — 0.3 Pre-formulated accords⁷ 13.8 13.8 13.5 14.0 Fragrance raw material⁸ 1.98 1.0 — 2.0 Fragrance raw material⁹ 0.02 0.04 0.01 — Carrier¹⁰ balance balance balance balance ¹1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(5-hydroxy-3-oxapentyl)-1-butanone. ²1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N-(5-hydroxy-3-oxapentyl)-1-butanone. ³2-(2,4-dimethyl-3-cyclohexen-1-yl)-3-(1-methylethyl)4-oxazolidinecarboxylic acid methyl ester. ⁴2-(6-methyl-5-hepten-2-yl)-3-(1-methylethyl)-4-oxazolidinecarboxylic acid methyl ester. ⁵Tris(geranyl) orthoformate. ⁶Benzyl bis(geranyl) orthoformate. ⁷Admixture of one or more fragrance raw materials which is enhanced by the presence of said fragrance delivery system. ⁸Lillial. ⁹γ-decalactone. ¹⁰Admixtures of ethanol and water ranging from about 100:0 to 50:50 by weight. 

1. A fragrance delivery system comprising: A) from about 0.01% by weight, of a pro-fragrance component which comprises pro-fragrances or pro-accords selected from at least two of the following: i) aldehyde and ketone releasing pro-fragrances; ii) β-amino pro-fragrances; and iii) orthoester pro-accords; and B) the balance carriers and other adjunct ingredients.
 2. A composition according to claim 1 further comprising a fragrance raw material component selected from the group consisting of at least 1% by weight, of a mixture of one or more base note fragrances; at least 1% by weight, of a mixture of one or more top or middle note fragrances; and mixtures thereof.
 3. The composition according to claim 1; wherein said aldehyde or ketone releasing pro-fragrance component has the formula:

wherein said pro-fragrance or pro-accord releases an aldehyde or a ketone fragrance raw material, wherein X is oxygen or sulfur; R is: i) C₆-C₂₂ substituted or unsubstituted linear alkyl; ii) C₆-C₂₂ substituted or unsubstituted branched alkyl; iii) C₆-C₂₂ substituted or unsubstituted linear alkenyl; iv) C₆-C₂₂ substituted or unsubstituted branched alkenyl; v) C₆-C₂₂ substituted or unsubstituted cycloalkyl; vi) C₆-C₂₂ substituted or unsubstituted branched cycloalkyl; vii) C₆-C₂₂ substituted or unsubstituted cycloalkenyl; viii) C₆-C₂₂ substituted or unsubstituted branched cycloalkenyl; ix) C₆-C₂₂ substituted or unsubstituted aryl; x) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl; xi) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl; xii) and mixtures thereof; R¹ is: i) hydrogen; ii) C₁-C₁₀ substituted or unsubstituted linear alkyl; iii) C₃-C₁₀ substituted or unsubstituted branched alkyl; iv) C₂-C₁₀ substituted or unsubstituted linear alkenyl; v) C₃-C₁₀ substituted or unsubstituted branched alkenyl; vi) C₃-C₁₅ substituted or unsubstituted cycloalkyl; vii) C₄-C₁₅ substituted or unsubstituted branched cycloalkyl; viii) C₄-C₁₅ substituted or unsubstituted cycloalkenyl; ix) C₅-C₁₅ substituted or unsubstituted branched cycloalkenyl; x) C₆-C₁₅ substituted or unsubstituted aryl; xi) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl; xii) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl; R and R¹ can be taken together to form a substituted or unsubstituted ring having in the ring from 3 to 10 carbon atoms; and each R², R³, R⁶ and each R⁴ and R⁵ pair are independently: i) R¹; ii) hydroxyl; iii) a carbonyl comprising unit having the formula: —(CH₂)_(x)COR⁷ wherein R⁷ is:  a) —OH;  b) —OR⁸ wherein R⁸ is hydrogen, C₁-C₁₅ substituted or unsubstituted linear alkyl, C₁-C₁₅ substituted or unsubstituted branched alkyl, C₂-C₂₂ substituted or unsubstituted linear alkenyl, C₃-C₂₂ substituted or unsubstituted branched alkenyl, or mixtures thereof; or R⁸ is M, wherein M is a water soluble cation of sufficient charge to render neutrality;  c) —N(R⁹)₂ wherein R⁹ is hydrogen, C₁-C₆ substituted or unsubstituted linear alkyl, C₃-C₆ substituted or unsubstituted branched alkyl, or mixtures thereof;  d) C₁-C₂₂ substituted or unsubstituted linear alkyl;  e) C₁-C₂₂ substituted or unsubstituted branched alkyl;  f) C₂-C₂₂ substituted or unsubstituted linear alkenyl;  g) C₃-C₂₂ substituted or unsubstituted branched alkenyl;  h) C₃-C₂₂ substituted or unsubstituted cycloalkyl;  i) C₆-C₂₂ substituted or unsubstituted aryl;  j) C₆-C₂₂ substituted or unsubstituted heterocyclicalkyl;  k) C₆-C₂₂ substituted or unsubstituted heterocyclicalkenyl;  the index x is from 0 to 22; iv) alkyleneoxy units having the formula: —(CR¹⁰R¹¹)_(y)(CHR¹²CHR¹³O)_(z)R¹⁴ wherein each R¹⁰, R¹¹, and R¹² is independently;  a) hydrogen;  b) —OH;  c) C₁-C₄ alkyl;  d) or mixtures thereof; R¹³ is:  a) hydrogen;  b) C₁-C₄ alkyl;  c) or mixtures thereof; R¹⁴ is:  a) hydrogen;  b) C₁-C₄ alkyl;  c) or mixtures thereof; R¹⁰ and R¹¹ can be taken together to form a C₃-C₆ spiroannulated ring, carbonyl unit, or mixtures thereof; y has the value from 0 to 10, z has the value from 1 to 50; v) any two R², R³, R⁴, R⁵, or R⁶ units can be taken together to form: a) a carbonyl moiety; b) a C₃-C₆ spiroannulated ring; c) a heterocyclic aromatic ring comprising from 5 to 7 atoms; d) a non-heterocyclic aromatic ring comprising from 5 to 7 atoms; e) a heterocyclic ring comprising from 5 to 7 atoms; f) a non-heterocyclic ring comprising from 5 to 7 atoms; g) or mixtures thereof; vi) and mixtures thereof; and the index n is an integer from 1 to 3; b) wherein said β-amino pro-fragrance component, has the formula:

wherein G¹ is C₁-C₄ alkyl, —CN, —C(O)Y¹, —CO₂Y¹, Y², and mixtures thereof; G² is C₁-C₄ alkyl, —CN, —C(O)Y¹, —CO₂Y², and mixtures thereof; Y¹ and Y² are each independently C₁-C₄ alkyl, or a unit having the formula:

wherein R⁶, R⁷, and R⁸ are each independently hydrogen, C₁-C₄ alkyl, and mixtures thereof; R⁶ and R⁷ can be taken together to form an exocyclic double bond with the ring; any two R⁶ and R⁷, or an R⁶ and R⁷ with an R⁸ can be taken together to form an endocyclic double bond within the ring; two or more R⁶, R⁷, and R⁸ units may be taken together to form one or more C₃-C₇ fused rings, bicyclic rings, or spiroannular rings; m is from 1 to 5; provided one G¹ or G² is —C(O)Y¹, —CO₂Y¹, or —CN; R and R¹ are each independently hydrogen, C₁-C₂₂ substituted or unsubstituted, branched or unbranched alkyl, C₂-C₂₂ substituted or unsubstituted, branched or unbranched alkenyl, C₂-C₂₀ substituted or unsubstituted, branched or unbranched hydroxyalkyl, C₇-C₂₀ substituted or unsubstituted alkylenearyl, C₃-C₂₀ substituted or unsubstituted cycloalkyl, alkyleneoxy units having the formula: —(R⁴O)_(x)R⁵ wherein R⁴ is C₂-C₄ alkylene, R⁵ is hydrogen, C₁-C₄ alkyl, and mixtures thereof, x is from 1 to 6; C₆-C₂₀ aryl, C₅-C₂₀ heteroaryl comprising one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and mixtures thereof; R and R¹ can be taken together to form one or more aromatic or non-aromatic, heterocyclic or non-heterocyclic, single rings, fused rings, bicyclo rings, spiroannulated rings, or mixtures thereof, said rings comprising from 2 to 20 carbon atoms and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and mixtures thereof; and wherein said orthoester pro-accord has the formula:

wherein R is hydrogen, C₁-C₈ linear alkyl, C₄-C₂₀ branched alkyl, C₆-C₂₀ cyclic alkyl, C₆-C₂₀ branched cyclic alkyl, C₆-C₂₀ linear alkenyl, C₆-C₂₀ branched alkenyl, C₆-C₂₀ cyclic alkenyl, C₆-C₂₀ branched cyclic alkenyl, C₆-C₂₀ substituted or unsubstituted aryl, and mixtures thereof: R¹, R² and R³ are independently C₁-C₂₀ linear, branched, or substituted alkyl; C₂-C₂₀ linear, branched, or substituted alkenyl; C₅-C₂₀ substituted or unsubstituted cyclic alkyl; C₆-C₂₀ substituted or unsubstituted aryl, C₂-C₄₀ substituted or unsubstituted alkyleneoxy; C₃-C₄₀ substituted or unsubstituted alkyleneoxyalkyl; C₆-C₄₀ substituted or unsubstituted alkylenearyl; C₆-C₃₂ substituted or unsubstituted aryloxy; C₆-C₄₀ substituted or unsubstituted alkyleneoxyaryl; C₆-C₄₀ oxyalkylenearyl, and mixtures thereof; or a cyclic orthoester having the formula:

wherein at least one R⁴ or R⁵ is derived from a fragrance raw material alcohol, each X is —C(R⁶)₂— wherein each R⁶ is independently hydrogen, C₁-C₂₂ linear or branched alkyl, C₂-C₂₂ linear or branched alkenyl, C₆-C₂₂ substituted or unsubstituted aryl, and mixtures thereof, Y is —CR⁷R⁸—, C═O, and mixtures thereof, wherein R⁷ and R⁸ are independently hydrogen, hydroxyl, nitro, nitrilo, C₁-C₃₀ substituted or unsubstituted linear alkyl, C₃-C₃₀ substituted or unsubstituted branched alkyl, C₃-C₃₀ substituted or unsubstituted cyclic alkyl, C₂-C₃₀ substituted or unsubstituted linear alkenyl, C₃-C₃₀ substituted or unsubstituted branched alkenyl, C₃-C₃₀ substituted or unsubstituted cyclic alkenyl, C₂-C₃₀ substituted or unsubstituted linear alkynyl, C₃-C₃₀ substituted or unsubstituted branched alkynyl, C₆-C₃₀ substituted or unsubstituted alkylenearyl, C₆-C₃₀ substituted or unsubstituted aryl, C₂-C₂₀ substituted or unsubstituted alkyleneoxy, C₃-C₂₀ substituted or unsubstituted alkyleneoxyalkyl, C₇-C₂₀ substituted or unsubstituted alkylenearyl, C₆-C₂₀ substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof, or R⁷ and R⁸ can be taken together to form a spiroannulated ring or taken together with any R⁶ to form a fused ring, said spiroannulated or fused ring having from 3 to 8 carbons and optionally one or more heteroatoms in said ring, said ring further optionally substituted by one or more C₁-C₂₂ alkyl, C₁-C₂₂ alkenyl, C₆-C₁₂ aryl, C₆-C₂₂ alkylenearyl units, and mixtures thereof; m is from 0 to 14, p is from 0 to 14, and n is from 0 to 3; provided m+n+p is at least 1 and less than or equal to 14; and optionally, further comprising a fragrance raw material component selected from the group consisting of at least 1% by weight, of a mixture of one or more base note fragrances; at least 1% by weight, of a mixture of one or more top or middle note fragrances; and mixtures thereof.
 4. A composition according to claim 1 wherein said aldehyde or ketone releasing pro-fragrance component releases a fragrance raw material selected from the group consisting of 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, phenylacetaldehyde, methylnonyl acetaldehyde, 2-phenylpropan-1-al, 3-phenylprop-2-en-1-al, 3-phenyl-2-pentylprop-2-en-1-al, 3-phenyl-2-hexylprop-2-enal, 3-(4-isopropylphenyl)-2-methylpropan-1-al, 3-(4-ethylphenyl)-2,2-dimethylpropan-1-al, 3-(4-tert-butylphenyl)-2-methyl-propanal, 3-(3,4-methylenedioxyphenyl)-2-methylpropan-1-al 3-(4-ethylphenyl)-2,2-dimethylpropanal, 3-(3-isopropylphenyl)butan-1-al, 2,6-dimethylhep-5-en-1-al, n-decanal, n-undecanal, n-dodecanal, 3,7-dimethyl-2,6-octadien-1-al, 4-methoxybenzaldehyde, 3-methoxy-4-hydroxybenz-aldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 3,4-methylenedioxy-benzaldehyde, 3,4-dimethoxybenzaldehyde, and mixtures thereof.
 5. A composition according to claim 1 wherein said aldehyde or ketone releasing pro-fragrance component has the formula:

wherein R⁸ is hydrogen, C₁-C₁₅ substituted linear alkyl, C₁-C₁₅ unsubstituted linear alkyl, C₁-C₁₅ substituted branched alkyl, C₁-C₁₅ unsubstituted branched alkyl, C₂-C₂₂ substituted or unsubstituted linear alkenyl, C₃-C₂₂ substituted or unsubstituted branched alkenyl, or mixtures thereof.
 6. A composition according to claim 1 wherein said aldehyde or ketone releasing pro-fragrance component is selected from the group consisting of:

d) and mixtures thereof.
 7. A composition according to claim 1 further comprising at least 0.01% by weight, of a pro-accord which releases n+1 fragrance raw materials wherein n is the number of fragrance raw materials from which said pro-accord is formed, n is from 1 to
 3. 8. A composition according to claim 1 wherein said β-amino pro-fragrance component comprises a G² unit which is methyl and a G¹ unit which is —C(O)Y¹ wherein Y¹ is selected from the group consisting of: i) 2,6,6-trimethylcyclohex-2-enyl having the formula:

ii) 2,6,6-trimethylcyclohex-1-enyl having the formula:

iii) 2-methylene-6,6-dimethylcyclohexanyl having the formula:

iv) 2,6,6-trimethylcyclohex-3-enyl having the formula:

v) and mixtures thereof.
 9. A fragrance delivery system comprising: a) from about 0.1% by weight, of a β-amino ketone pro-fragrance selected from the group consisting of 1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(5-hydroxy-3-oxapentyl)-1-butanone, 1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N,N-bis(2-hydroxyethyl)-1-butanone, 1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-3-N-(5-hydroxy-3-oxapentyl)-1-butanone, and mixtures thereof; b) from about 0.2% by weight, of analdehyde releasing pro-fragrances selected from the group consisting of 2-(6-methyl-5-hepten-2-yl)-3-(1-methylethyl)-4-oxazolidinecarboxylic acid methyl ester, 2-(2,4-dimethyl-3-cyclohexen-1-yl)-3-(1-methylethyl)-4-oxazolidinecarboxylic acid methyl ester, and mixtures thereof; c) optionally from about 0.1% by weight, of one or more alcohol releasing pro-fragrances or pro-accords; d) from about 0.1% by weight, of one or more fragrance raw materials; e) optionally, from about 1% by weight, of pre-blended perfume ingredients of fragrance raw material accords; and f) the balance carriers.
 10. A composition according to claim 9 wherein said alcohol releasing pro-fragrances or pro-accords are selected from the group consisting of tris-geranyl orthoformate, tris(cis-3-hexen-1-yl) orthoformate, tris(phenylethyl) orthoformate, tris(undecavertyl) orthoformate, bis(citronellyl) ethyl orthoacetate, tris(citronellyl) orthoformate, tris(cis-6-nonenyl) orthoformate, tris(phenoxyethyl) orthoformate, tris(geranyl, neryl) orthoformate (70:30 geranylineryl), tis(9-decenyl) orthoformate, tris(3-methyl-5-phenylpentanyl) orthoformate, tris(6-methylheptan-2-yl) orthoformate, tris([4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-yl] orthofomate, tris[3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-yl] orthoformate, trismenthyl orthoformate, tris(4-isopropylcyclohexylethyl-2-yl) orthoformate, tris-(6,8-dimethylnonan-2-yl) orthoformate, tris-phenylethyl orthoacetate, tris(cis-3-hexen-1-yl) orthoacetate, tis(cis-6-nonenyl) orthoacetate, tris-citronellyl orthoacetate, bis(geranyl) benzyl orthoacetate, tris(geranyl) orthoacetate, tris(4-isopropylcyclohexylmethyl) orthoacetate, tris(benzyl) orthoacetate, tris(2,6-dimethyl-5heptenyl) orthoacetate, bis(cis-3-hexen-1-yl) amyl orthoacetate, and neryl citronellyl ethyl orthobutyrate, and mixtures thereof.
 11. A composition according to claim 9 wherein said alcohol releasing pro-fragrances or pro-accords are selected from the group consisting of bis(ethyl) bis(geranyl) orthocarbonate, bis(ethyl) bis(phenylethyl) orthocarbonate, bis(ethyl) bis(cis-3-hexenyl) orthocarbonate, bis(ethyl) bis(citronellyl) orthocarbonate, bis(ethyl) bis(linalyl) orthocarbonate, bis(ethyl) bis(menthyl) orthocarbonate, bis(dodecyl) bis(geranyl) orthocarbonate, and bis(dodecyl) bis(phenylethyl) orhocarbonate, and mixtures thereof.
 12. A composition according to claim 1 wherein said orthoester pro-accords release one or more fragrance raw material alcohols selected from the group consisting of 4-(1-methylethyl)cyclohexanemethanol, 2,4-diethyl-3-cyclohexen-1-ylmethanol, (2,4-dimethylcyclohex-1-yl)methanol, (2,4,6-trimethyl-3-cyclohexen-1-yl)methanol, 2-phenylethanol, 1-(4-isopropylcyclohexyl)-ethanol, 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol, 3-phenyl-2-propen-1-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl-2-buten-ol, 3-methyl-5-phenylpentan-1-ol, 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl-4-penten-2-ol, 2-methyl-4-phenylpentan-1-ol cis-3-hexen-1-ol, 3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-2,6-octadien-1-ol, 7-methoxy-3,7-dimethyloctan-2-ol, 6,8-dimethylnonan-2-ol, cis-6-nonen-1-ol, 2,6-nonadien-1-ol, 4-methyl-3-decen-5-ol, benzyl alcohol, 2-methoxy-4-(1-propenyl)phenol, 2-methoxy-4-(2-propenyl)phenol, and mixtures thereof.
 13. A composition according to claim 1 wherein said orthoester pro-accord is a pro-accord which comprises n fragrance raw materials, said fragrance raw materials having a molecular weight greater than or equal to about 100 g/mol and capable of releasing upon hydrolysis n+1 fragrance raw materials, provided said pro-accord a) has a molecular weight greater than or equal to about 300 g/mol; b) has a molecular weight at least two times greater than the lowest molecular weight fragrance raw material which comprises said pro-accord; and c) has a fragrance release half-life of greater than or equal to 0.1 hours at pH 5.3 and less than or equal to about 12 hours at pH 2.5 when measured in NaH₂PO₄ buffer; wherein n is an integer from 1 to
 3. 